Catalyst composition and olefin polymerization using same

ABSTRACT

Novel metal complexes, particularly chromium complexes, which contain at least one tridentate ligand are disclosed and prepared. Olefins, particularly ethylene, can be reacted to form butene and/or other homo- or co-oligomers and/or polymers with high α-olefin concentrations by contacting a metal catalyst which contains a transition metal, particularly chromium, complexes having per metal atom at least one tridentate ligand with N, O, or N and O coordinating sites.

FIELD OF THE INVENTION

This invention relates to novel metal complexes, particularly chromiumcomplexes, which contain at least one tridentate ligand for each metal.This invention also relates to an improved olefin polymerization processcatalyzed by a catalyst composition, which comprises such novel metalcomplexes. The polymerization process is particularly useful for making1-butene and a wide range of oligomeric and polymeric products havinghigh α-olefin concentrations.

BACKGROUND

Many linear olefins, particularly linear α-olefins, typically have avariety of valuable uses. For example, α-olefins, such as 1-hexene, canbe used in hydroformylation (so-called “OXO” process) to produceoxygenated products like alcohols and aldehydes. In addition to findinguses in specialty chemicals or as intermediates, α-olefins also can beused in polymerization processes as either a monomer or co-monomer toprepare polyolefins, or other polymers. For example, it has been widelyreported that 1-octene can form polymers or co-polymers, which may beused as effective drag reducing agents for transporting hydrocarbons inpipelines. It is therefore desirable to control the linearity of theproduct, or produce linear olefins, particularly linear α-olefins, inmost oligomerization or polymerization processes.

It is well known that mono-olefins, particularly lower α-olefins,particularly ethylene, propylene, and 1-butene can be oligomerized(including dimerized and trimerized) and/or polymerized by usinghomogeneous or heterogeneous catalyst systems comprisingcompounds-derived from transition metals such as titanium, zirconium,vanadium, chromium, nickel and/or other metals, either unsupported or ona support such as alumina, silica, silica-alumina, titania, otherrefractory metal oxides, and other similar materials. Even dienemonomers such as 1,3-butadiene may be oligomerized or polymerized togive various products such cyclooctadienes. These polymerizationcatalyst systems frequently are used with an organometallic co-catalyst,such as organoboron, organoaluminum and/or organotin compounds.

Many catalyst systems are usually not very selective in the productionof oligomeric or polymeric olefinic products in terms of molecularweight distribution, linearity of the carbon-carbon backbone, branching,location of the double bond(s) in the product, and incorporation ofco-monomers, if any, into the product. Some reported homogeneousorganometallic catalyst systems tend to have lower activities, higherconsumptions of co-catalysts, but they can produce lower molecularweight oligomers or polymers with a narrow molecular weightdistribution.

As a result, there is always a need of improving the catalyst systems tohave better catalytic properties in terms of controlling specificoligomerization or polymerization of specific olefins or diolefins toproduce products with the desired or targeted physical and chemicalproperties.

SUMMARY OF THE INVENTION

It is one objective of the present invention to provide a polymerizationprocess for making a product, the polymerization process comprisescontacting at least one olefin in a feed, with or without a medium, witha catalyst and a co-catalyst, followed by recovering the product,wherein the catalyst comprises a metal-tridentate ligand complexcomprising a metal, preferably a transition metal, one or moretridentate ligands (such as FORMULA A) having at least two differentelements for the three coordinating sites in each tridentate ligand, theelements are independently selected from the group consisting ofnitrogen, phosphors, oxygen, and sulfur, and wherein themetal-tridentate ligand complex has a formula as FORMULA B.

It is another object that the olefin to be polymerized includes, but isnot limited to, mono-olefins (α-olefins and internal olefins; linear andbranched olefins) like ethylene, propylene, 1-butene, cis-2-butene,trans-2-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,1-hexene, 1-heptene, 1-octene, vinylcyclohexene, cyclopentene,methylcyclopentene (1-, 2-, 3- or mixtures), 1-octadecene, and mixturesof mono-olefins; dienes like 1,3-butadiene, isoprene, 1,4-pentadiene,1,3-hexadiene, 1,4-hexadiene and 1,5-hexadiene, 4-vinylcyclohexene,vinylnorbornene, norbornadiene, and mixtures of dienes; vinyl-aromaticcompounds such as 1- or 2-vinylnaphthalene, 2- or 4-vinylpyridine,styrene and substituted styrenes like o-methylstyrene, m-methylstyrene,p-methylstyrene, p-ethylstyrene, divinylbenzene, and p-t-butylstyrene;and mixtures thereof, and mixtures of mono-olefins, dienes and/orvinyl-aromatic compounds.

It is a further object to provide a catalyst composition which comprisesa metal-tridentate ligand complex having a structure of FORMULA B,wherein M consists essentially of an element selected from the groupconsisting of manganese, chromium, vanadium, nickel, and mixturesthereof; the co-catalyst comprises one or more aluminum alkyl compoundsor organoboron compounds, or mixtures thereof; and the product comprisesα-olefins, which can be linear, branched, or mixtures thereof. Inanother embodiment, the product can be characterized by havingSchulz-Flory constants (K) in the range of from about 0.4 to about 0.98,preferably from about 0.5 to about 0.9, more preferably from about 0.55to about 0.8.

It is another object to provide an ethylene dimerization process formaking 1-butene, the dimerization process comprises contacting ethylenein a feed, with or without a medium, with a catalyst and a co-catalyst,followed by recovering 1-butene, wherein the catalyst comprises ametal-tridentate ligand complex comprising a transition metal, one ormore tridentate ligands (such as FORMULA A) having nitrogen for allthree coordinating sites in the tridentate ligand, and wherein themetal-tridentate ligand complex has a formula as FORMULA B. Depending onR¹¹ and R¹⁵, high 1-butene purity (in excess of 98%, preferably inexcess of 99% or higher, among the butene isomers) may be obtained.

Another object of the present invention to provide a catalystcomposition which comprises a metal-tridentate ligand complex comprisinga stricture of FORMULA B.

It is a further object to provide a catalyst composition which comprisesa metal-tridentate ligand complex comprising a structure of FORMULA B,wherein Q¹ and Q² are nitrogen, Q³ is oxygen, and R⁴ does not exist; R¹and R³ are independently selected from C₁ to C₅ alkyl groups; R² isselected from 1-ring aryl groups; R⁵ R⁶, and R⁷ are independentlyselected from H and C₁ to C₅ alkyl groups; L is selected from F, Cl, Br,I and mixtures thereof; and q is 2.

It is another object of the present to provide a chromium chloridecomplex containing6-[1-{(2,6-dimethylphenyl)imino}ethyl]-2-acetylpyridine.

It is yet another object of the present to provide a chromium chloridecomplex containing6-[1-{(2,6-diisopropylphenyl)imino}ethyl]-2-acetylpyridine.

It is still another object to provide a method for making the metalcomplexes with suitable transition metal starting materials and suitableligands tinder conditions effective to produce such complexes.

It is yet another object to provide a method for making the suitabletridentate ligands, which are useful for making the metal complexes.

Another object is to provide a multi-component catalyst systemcomprising (a) at least one first component consisting essentially of anethylene or propylene dimerization or trimerization catalyst comprisinga metal-tridentate ligand complex described herein such as FORMULA Bcontaining a first transition metal, and with nitrogen for all threecoordinating sites, and (b) at least one second component consistingessentially of an ethylene or propylene polymerization catalyst such asa Ziegler-Natta catalyst, a precursor of the Ziegler-Natta catalyst, ametallocene, a precursor of the metallocene, and mixtures thereof. Thesecond component contains a second transition metal. It is preferred touse one or more co-catalysts such as organometallic compounds with themulti-component catalyst system to produce ethylene or propylenepolymers.

A further object is to provide an olefin polymerization process using amulti-component catalyst system, an organometallic co-catalyst, and theolefin being selected from ethylene, propylene and mixtures thereof in afeed tinder condition effective to produce polymers, wherein themulti-component catalyst system comprises (a) at least one firstcomponent consisting essentially of an ethylene or propylenedimerization or trimerization catalyst, which comprises ametal-tridentate ligand complex described herein, such as FORMULA B andcontaining a first transition metal, with nitrogen for all threecoordinating sites, and (b) at least one second component consistingessentially of an ethylene or propylene polymerization catalyst such asa Ziegler-Natta catalyst, a precursor of the Ziegler-Natta catalyst, ametallocene, a precursor of the metallocene, and mixtures thereof. Thesecond component contains a second transition metal. The polymers arecharacterized by being a product selected from the group consisting ofpolyethylene (PE), low density polyethylene (LDPE), linear low densitypolyethylene (LLDPE), polypropylene (PP), wax, and mixtures thereof.

Other additional objects and advantages will become apparent to andappreciated by those skilled in the art by reading the disclosuresherein.

DETAILS OF THE INVENTION

The present invention relates to novel metal-ligand, particularlymetal-tridentate ligand complexes, the method for making such complexes,and olefin polymerization processes using catalysts comprising suchcomplexes. The present invention also relates to a novel multi-componentcatalyst system, which system comprises (a) at least one first componentconsisting essentially of such a metal-multidentate ligand complex and(b) at least one second component consisting essentially of at least oneZiegler-Natta catalyst or its precursor or a metallocene or ametallocene precursor or mixtures thereof; and a polymerization processusing such multi-component catalyst in the presence of an organometallicco-catalyst. For the instant invention and disclosure, the term“polymerization” Is used interchangeably, unless otherwise specificallyspecified or claimed, with the term “oligomerization” to encompassgenerally (co-)dimerization, (co-)trimerization, homo- orco-oligomerization, and homo- or co-polymerization of one or moreolefins (alkenes), vinyl aromatics, and/or diolefins to form(co-)dimers, (co-)trimers, homo- or co-oligomers and/or homo- orco-polymers of the olefin(s) in a feed.

Suitable metal-ligand complexes comprise a metal, a bidentate,tridentate or multidentate ligand, other ligands/moieties/counter-ionsto balance the electrical (ionic) charge so that the whole complex isneutral and/or the formal electron count is satisfied, and optionallysolvent molecules. Two or more metal atoms, same or different and withor without direct metal-metal bonds may be present in a complex.

Unless a specific ligand is used or referred to, the word “multidentate”is used to denote a ligand having two, three or more coordinating sites.Many ligands having different number and/or type of coordinating sitescan be used for the present invention. Tridentate ligands are preferredfor the present invention. It is more preferred to have at least twodifferent elements (for instance, N and O) for the three coordinatingsites of the three per tridentate ligand. For ethylene dimerization to1-butene, it is preferred to have nitrogen for all of the threecoordinating sites; it is more preferred to have either R¹¹ or R¹⁵ beingselected from the group consisting of methyl (Me), ethyl (Et), n-propyl(nPr), iso-propyl (iPr), and n-butyl (nBu). For making wax, it ispreferred to have either R¹¹ or R¹⁵ being a t-butyl group.

A more preferred tridentate ligand has the following FORMULA A.

wherein

-   Q¹, Q², and Q³: independently selected from O, S, N, and P;-   R¹ and R³: independently selected from H, C₁ to C₂₀ alkyl groups 1-,    2- or 3- (i.e. 1–3) ring aryl groups and substituted aryl groups;-   R² and R⁴: if Q² or Q³ is O or S, none    -   if Q² or Q³ is either N or P, independently selected from H, C₁        to C₂₀ alkyl groups, 1-, 2- or 3-ring aryl groups and        substituted aryl groups;-   R⁵, R⁶, and R⁷: independently selected from H, C₁ to C₂₀ alkyl    groups; and R⁷ does not exist if the carbon to which it is attached    is not present.

It is understood that with or without R⁷ and the associate carbon towhich it is attached, the ring containing Q¹ is characterized by andshould have some aromatic characteristics. For instance, Q¹ may beoxygen and the ring is based on a five-membered ring furan structure.

Depending primarily on the starting materials for the metal(s) and thenature of the multidentate ligands, there may be other ligands ormoieties or ions present in the complex to balance the electrical(ionic) charges and/or formal electron counts. For instance, if chromium(II) chloride, or CrCl₂, is used as the starting material for chromium,chloride will be present in the metal-ligand complex. The number andtype of the ligands present may vary, depending on the oxidation stateof the metal in the starting material, whether there is any redoxreaction taking place, whether the multidentate ligand is used in anionic form with its own counter-ions, the number of metals in thecomplex, and other reaction conditions. There may be other reactants,either organic or inorganic, such as acids, salts, bases, and mixtureswith different ions present in the reaction, which may end up in thefinal product.

“L” can be any anions or neutral molecules such as CO. Some non-limitingexamples of “L” include CO, H, hydroxide (OH), halides andpseudo-halides, chlorate, chlorite, phosphate, phosphite, sulfate,sulfite, nitrate, amides, alkoxides and their analogues (including thosederived from glycols, thiols and phenols), carboxylates (includingdicarboxylates and substituted carboxylates such as 2-ethylhexanoate andtriflates), hydrocarbyls like alkyls (such as methyl, ethyl, andothers), alkenyls, aryls (such as phenyl, methylphenyls, and the like),and mixtures thereof. More examples are further disclosed below inassociation with FORMULA B.

Because the complex preparation is generally more convenient carried outin a solution, there may be one or more solvents present during thereaction and/or in the final complex. If one of the reactants is aliquid or the reaction is conducted in a melt-phase, a solvent is notneeded for this convenience. As long as a solvent or solvent mixturedoes not interfere with the metal-multidentate ligand complex formation,it can be used. Depending on the nature of the solvent, the metalcomplex and the recovery methods/conditions, one may find that there isno solvent in the recovered complex. It is also possible to find bychemical analyses that the number of solvent molecules per metal may befractional.

Examples of a suitable solvent include both organic and inorganicsolvents and their mixtures, such as alcohols (methanol, ethanol, 1- or2-propanol, sec-butanol, n-butanol, t-butanol, ethylene glycol,propylene glycol, mixtures thereof, or mixtures with water), ethers(dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran orTHF, tetrahydropyran, 1,3-dioxane, 1,4-dioxane and mixtures thereof),glycol ethers, esters (methyl acetate, ethyl acetate, etc), thioethers,halogenated hydrocarbons (such as CFC's [chlorofluoro hydrocarbons],methyl chloride, methyl bromide, methyl iodide, dichloromethane,dibromomethane, chloroform, ethylene dichloride and others), aliphaticand aromatic hydrocarbons, and mixtures thereof. Many of these solvents,such as oxygenated solvents (an ether like THF is ail example) can becharacterized as Lewis base solvents (i.e. electron pair donatingsolvents). Additional examples are disclosed below in FORMULA B.

A metal-tridentate ligand complex suitable for the present invention isof the following general FORMULA B:

wherein

-   Q₁, Q², and Q³: independently selected from O, S, N, and P;-   R¹ and R³: independently selected from H, C₁ to C₂₀ alkyl groups,    1-, 2- or 3- (i.e. 1–3) ring aryl groups and substituted aryl    groups;-   R² and R⁴: if Q² or Q³ is O or S, none    -   if Q² or Q³ is either N or P, independently selected from H, C₁        to C₂₀ alkyl groups, 1-, 2- or 3- (i.e. 1–3) ring aryl groups        and substituted aryl groups;-   R⁵, R⁶, and R⁷: independently selected from H, C₁ to C₂₀ alkyl    groups;-   M: a first transition metal selected from the group consisting of    Cr, Mn, V, Ni, Ti, Zr, Hf, Ta, and mixtures thereof;-   L: each L independently selected from the group consisting of F, Cl,    Br, I, C₁ to C₂₀ alkyl, C₅ to C₁₄ aryl, nitrate, OR²¹, OC(═O)R²²;    R²³; CN; SCN, CO, H, wherein R²¹, R²², and R²³ are independently    selected from the group consisting of H, C₁ to C₂₀ alkyl groups,    substituted alkyl groups, 1-, 2- or 3-ring aryl groups, substituted    aryl groups, and silyl groups;-   solvent selected from the group consisting of ethers, polyethers,    esters, alcohols, halogenated hydrocarbons, and mixtures thereof;-   q 0–5 (integer) to balance overall electrical charge-   m 0–10 (integer or fractional).

As understood from the chemical formula/stricture of FORMULA B, themetal complex must comprise at least one metal, preferably a firsttransition metal and at least one tridentate ligand. As discussedearlier, the number of other ligands (L) would depend on the netelectric (used interchangeably with ionic) charge of the M-Ligand so asto make the entire formula neutral. Also as discussed earlier, thenumber of solvent molecules may vary, depending on the complex,solvent(s), preparation method and many ether factors and “m” need notbe an integer as determined by chemical analyses. In other words, “m”may be fractional (per metal).

The scope of the present invention encompasses many different metals, M,particularly transition metals, such as titanium, zirconium, hafnium,vanadium, niobium, tantalum, chromium, manganese, iron, nickel, cobalt,and mixtures thereof. It is preferable that M consists essentially of anelement selected from the group consisting of chromium, manganese,vanadium, and mixtures thereof Chromium is a more preferred metal.

Many different sources of these metals may be used to prepare themetal-ligand complexes. These sources include, as discussed earlier,metal halides, pseudo halides, carboxylates, alkoxides, phenoxides,nitrates, sulfates, phosphates, chlorates, organometallic compounds,metal carbonyls, metal clusters and mixtures thereof. Differentoxidation states may be used. For instance, many of these materials maybe purchased from commercial sources such as Aldrich Chemical Company,Fluka Chemical Company, Alfa AESAR Chemical Company, etc.

More specifically for chromium (oxidation states from 0 to VI), thefollowing materials may be used: chromium(II) chloride, chromium(III)chloride, chromium(II) fluoride, chromium(III) fluoride, chromium (II)bromide, chromium(III) bromide, chromium(II) iodide, chromium(III)iodide, chromium(II) acetate, chromium (III) acetate, chromium(III)acetylacetonate, chromium(II) 2-ethylhexanoate, chromium (II) triflate,chromium(III) nitrate, Cr(CO)₆, and mixtures thereof.

As mentioned briefly above, L can be any suitable anion or neutralmolecule. If one or more “L's” are needed to balance the charge ofFORMULA B to zero, then each “L” is independently selected from thegroup consisting of CO, H, halides (F, Cl, Br, I,), nitrate, alkoxidesor phenoxides (OR²¹) carboxylates [OC(═O)R²²], R²³, CN, SCN, and CO.R²¹, R²², and R²³ are independently selected from the group consistingof H, C₁ to C₂₀ alkyl groups, substituted alkyl groups, 1-, 2- or 3-ringaryl groups, substituted aryl groups and other hydrocarbyl groups suchas alkenyl groups. The substituents on the alkyl or aryl groups include,but are not limited to alkyls, aryls, halides, silyl groups, aminogroups, alkoxy groups and mixtures thereof. In addition, L can also beselected from hydrocarbyls such as alkyl, alkenyl, or aryl groups.Examples of suitable alkyl groups include, but are not limited to C₁ toC₂₀ linear or branched alkyls, such as methyl, ethyl, n-propyl,isopropyl, n-butyl, iso-butyl, t-butyl, sec-butyl, 1-octyl groups andothers. C₃ to about C₂₀ linear or branched alkenyl groups also may beused. Examples of suitable aryl groups include, but are not limited toC₅ to C₁₄ aryls such as 4-pyridyl, 2-pyridyl, phenyl, p-methylphenyl,o-methylphenyl, etc. It is preferred to have halogens as L. It is morepreferred the L is or consists of or consists essentially of Cl.

If two or more L's are needed, then they can be independently selectedfrom all of those described and disclosed above, or from moietiescontaining two or more such groups. For instance, if two L's are neededor preferred, then a glycol type (LL), i.e. —O—CH₂—CH₂—O— or—O—CH₂—CH(CH₃)—O— can be used. It is also within the scope of theinvention to have mixed (LL′) type where the chelating groups are notidentical. The above propylene glycol type is one example. Otherexamples include moieties with mixed alkoxides with phenoxides and/orcarboxylates.

It is preferred that Q¹ is nitrogen (N). Hydrogen and C₁ to C₅ alkylgroups such as methyl or ethyl are preferred, independently, for R⁵, R⁶,and R⁷. More preferably, R⁵, R⁶, and R⁷ are all H.

Q¹, Q², and Q³ can all be nitrogen (N) in FORMULA B. In a preferredembodiment, not all of Q¹, Q², and Q³ are the same, particularly formaking waxes or polyethylenes. It is more preferred to have (a) N forQ¹, N for Q², and O for Q³; or (b) O for Q¹, N for Q², and O for Q³.

Preferably Q² is nitrogen (N). When Q¹ and Q² are both nitrogen, it ispreferred that Q³ is oxygen or sulfur, except for ethylene dimerizationto high purity 1-butene or 2-butenes or mixtures thereof. In this case,R⁴ does not exist (i.e. none) to satisfy the valence requirement ofoxygen or sulfur. Ethylene can be dimerized to butene by using thepresent invention. For ethylene dimerization to 1-butene in excess of98%, preferably in excess of 99% or higher purity among butene isomers,it is preferred to have Q¹, Q², and Q³ all being nitrogen, andpreferably R² and R⁴ are phenyl and the corresponding R¹¹ is preferredto be independently selected from the group consisting of methyl, ethyl,n-propyl or isopropyl. For ethylene dimerization to butenes (1-butene,cic-2-butene, trans-2-butene mixture), it is preferred to have Q¹, Q²,and Q³ all being nitrogen; and preferably R² and R⁴ are both phenyl andthe corresponding two R¹¹ groups are preferably hydrogen. (see FORMULA Cbelow)

Regardless which elements are selected for Q² and Q³, it is preferred tohave selected from C₁ to C₅ alkyl groups, 1-ring aryl and substitutedaryl groups (i.e. phenyl groups) selected independently for R¹ and R³.Methyl group is more preferred for both R¹ and R³.

If either or both of Q² and Q³ are nitrogen, then it is preferred tohave phenyl groups for R² and/or R⁴ attached to the nitrogen and thephenyl groups, selected independently for Q² and/or Q³, are shown asfollows (FORMULA C)

wherein R¹¹, R¹², R¹³, R¹⁴, and R¹⁵ are individually selected from H, C₁to C₂₀ alkyl groups, substituted C₁ to C₂₀ alkyl groups, 1–3 ring arylgroups, substituted 1–3 ring aryl groups, F, Cl, Br, I, amino groups,silyl groups such as Si(CH₃)₃, Si(phenyl)₃, and the like. Many othersubstituents such as nitro groups can also be used for making themetal-tridentate ligand complexes. However, if the complexes are used ascatalysts for polymerization reactions, all of the above-mentioned R'sshould not have functional groups that would interfere with thepolymerization reactions themselves or other components such asco-catalysts, if present. It is preferred to have H for R¹², R¹³, andR¹⁴. It is also preferable to have a C₁–C₅ alkyl group or H for eitheror both of R¹¹ and R¹⁵. More preferred R¹¹ and R¹⁵ are selectedindependently from the group consisting of H, methyl, ethyl, n-propyl,iso-propyl, and n-butyl groups. As already discussed. Q¹, Q² and Q³ arepreferably all nitrogen and only one of R¹¹ and R¹⁵ is H when ethylenedimerization to 1-butene (in excess of 98%, or preferably in excess of99% or even higher purity) is the preferred polymerization reaction.When 2-butenes or butene mixtures are the preferred ethylenedimerization products, both R¹¹ and R¹⁵ are preferred to be H.

When the metal M is selected from the group consisting of manganese,chromium, vanadium, and mixtures thereof, it is preferred to have H,methyl, iso-propyl, and/or n-butyl groups for both R¹¹ and R¹⁵ in orderfor the complexes to be better catalysts, particularly as catalysts forethylene polymerization or co-polymerization in the presence of aco-catalyst such as aluminum alkyls, aluminum alkyl halides, alumoxanesSuch as MAO or MMAO (modified MAO, some are commercially availableproducts from Akzo Nobel in heptane solutions.).

FORMULA B is a preferred embodiment of the present invention. As FORMULAA INDICATES, it is also within the scope of the present invention that afive-membered ring containing Q¹ may be used as part of the tridentateligand. In this case. R⁷ and the carbon to which it is attached inFORMULA B do not exist. It is still contemplated that the five-memberedring portion possesses aromatic characteristics. Depending on Q¹, theelectrical (ionic) charge of the entire metal complex has to be balancedto zero with a proper number of “L's” present.

Another embodiment of the present invention provides a multidentateligand with 2, 4, 5 or 6 coordinating atoms. While the threecoordinating atoms in FORMULA B are more or less on the same plane, i.e.co-planar, this may not be the case for all of the coordinating atoms ina tetra-, penta-, or hexa-dentate ligand.

As already mentioned briefly, a preferred solvent includes, but is notlimited to, coordinating solvents (i.e. Lewis base type solvents orelectron pair donating solvents), particularly polar oxygenated solventssuch as alcohols, ethers, esters, ketones, or mixtures. Some water maybe present with the alcohols, ethers, glycols, or other water-miscibleorganic solvents. Examples of suitable polar oxygenated solventsinclude, but are not limited to, dimethyl ether, diethyl ether, methylethyl ether, monoethers or diethers of glycols such as dimethyl glycolether, furans, dihydrofuran, substituted dihydrofurans, tetrahydrofuran(THF), tetrahydropyrans, (1,3 and/or 1,4-) dioxanes, methyl acetate,ethyl acetate, methyl ethyl ketone, acetone, and the like and mixturesthereof. Acyclic or cyclic polyethers such as poly(ethylene glycol)ethers, crown ethers (such as 12-crown-4 or 18-crown-6) and theirmixtures can also be used even though some of them may be much moreexpensive than others.

THF is a more preferred solvent, particularly when CrCl₂ is used as astarting material with6-[1-{(2,6-dimethylphenyl)imino}ethyl]-2-acetylpyridine and6-[1-{(2,6-diisopropylphenyl)imino}ethyl]-2-acetylpyridine as theligands. Other polar solvents such as 1,4-dioxane, tetrahydropyran,halogenated hydrocarbons (chloroform or dichloromethane), thioethers,and the like also may be used alone or as mixtures between themselves orwith other solvents, particularly those disclosed herein.

The following general procedure may be used to prepare the metalcomplexes. A first amount of a metal starting material, such as ahalide, and a second amount of a ligand, such as6-[1-{(2,6-dimethylphenyl)imino}ethyl]-2-acetylpyridine are mixed in asuitable solvent under conditions effective to produce the product. Themixture is thoroughly mixed with proper agitation or gas purging for aperiod from one minute to 30 days. Then, optionally the mixture may belet stand for an additional one minute to thirty days without agitation.If the product is an insoluble solid in the reaction solvent, it isfiltered and optionally washed with the same solvent or another solvent,preferably a more volatile one. The washed product is then placed undervacuum or in a flowing gas condition to remove all the volatiles. If theproduct is soluble in the reaction solvent under the conditions, one caneither remove part or all of the solvent, and/or cool the reactionmixture to a lower temperature to precipitate the product solid followedby filtration and optional washing. The solid can also be recovered byremoving the solvent by other techniques such decantation known to thoseskilled in the art. The product is then weighed to determine yield andcharacterized by chemical analyses, NMR and/or ICP to determine itschemical composition and structure. In the rare event that the complexis a liquid at room temperature, the product can be recovered orpurified by distillation, chromatography or other means known in theart.

As shown in FORMULA B, it is most likely that the metal-tridentateligand complex has a ligand to metal molar ratio of 1:1. For preparationof the complex, the molar ratio of the ligand to the metal (whatever thestarting material may be) should be in the range of 1:10 to 10:1;preferably 1:5 to 5:1; more preferably 1:2 to 2:1. Availability, costs,desired product, and product separation/purification are the majorfactors to be considered for selecting a suitable molar ratio.

The complex formation reaction can be carried out at a temperature inthe range of from about −20° C. to about 150° C., preferably form about0° C. to about 90° C., and more preferably from about 15° C. to about50° C. The pressure is normally not a critical factor. It is convenientto use ambient pressure, but sub- or super-atmospheric pressures may beused. Some of the starting materials and/or products may be air and/ormoisture sensitive. It is therefore preferred to carry out the reactionand/or the product recovery and/or the product purification steps in adried atmosphere such as nitrogen, argon, helium, neon, krypton,methane, ethane, propane, and mixtures thereof. If there are no otherconcerns, air, carbon monoxide, carbon dioxide, hydrogen may also beused individually, or as mixtures thereof, or as mixtures with inertgases or other gases. It may also be easier to keep moisture and oxygenout by having a reactor or reaction system pressure slightly higher thanthe ambient (atmospheric) pressure.

If it is desirable to support the metal complex on a carrier, there aremany inorganic and/or organic carriers within the scope of the presentinvention. The selection depends on the nature of the metal complex, theco-catalyst if any, the desired polymerization reaction and othersimilar factors. It is preferred that the support provide some benefitsto the catalyst system chemically or catalytically, but this is notrequired. There may be other reasons to select a particular support, forinstance easier product purification, lower cost, cheaper manufacturingprocess, etc. Inorganic carriers suitable for the present inventioninclude, but are not limited to, crystalline or amorphous silicas(including those disclosed in U.S. Pat. No. 6,107,236), crystalline oramorphous aluminas, zeolites (both natural and synthetic ones such asZSM-5, ZSM-11, etc), crystalline or amorphous silicoaluminas,silicoaluminophosphates (SAPOs), metalaluminophosphates (MEAPOs),aluminophosphates (ALPOs), titanium oxide (titania), zirconium oxide(zirconia), magnesium oxide, magnesium chloride, manganese chloride, andthe like and mixtures thereof. Some typical examples of suitablesupports can be found in “Heterogeneous single site catalysts for olefinpolymerization” Gregory G. Hlatky, Chemical Reviews, 100, pp 1347–1376(2000).

A metal-multidentate ligand complex may be placed on the supports by anumber of known methods. The support can be present during or after themetal complex is made from the starting materials. Non-limiting examplesinclude incipient wetness, in-situ mixing, solution impregnation,dry-mixing/admixing/blending, ion-exchange, sublimation,co-precipitation, and combinations and/or repetitions thereof.

As already mentioned hereinabove, the present invention also relates toa novel multi-component catalyst system for olefin, particularlyethylene or propylene or mixtures thereof, polymerization process. Thismulti-component catalyst system comprises (a) at least one firstcomponent consisting essentially of one or more ethylene or propylenedimerization and/or trimerization catalyst comprising themetal-multidentate ligand complexes, particularly the chromium basedcomplexes as described herein (such as those encompassed by FORMULA B)and preferably all coordinating sites are nitrogen; and (b) at least onesecond component consisting essentially of an olefin polymerizationcatalyst selected from the group consisting of Ziegler-Natta catalyst,its precursor, a metallocene or metallocene precursor, a secondmetal-tridentate ligand complex wherein it is different from the one(s)used in (a) and/or not all three coordinating sites are the same, andmixtures thereof. This catalyst system, supported or unsupported, may beused preferably with a co-catalyst containing at least oneorganometallic compound as disclosed herein to polymerize olefins,particularly α-olefins like ethylene or propylene or mixtures ofethylene and propylene to a product. The product may be wax, PE, PP,LDPE, LLDPE, and the like, and mixtures thereof. Without being bound bya particular theory, it is expected that the first component willdimerize or trimerize ethylene and/or propylene to butene, pentene,hexane, heptane, octane and/or nonene. These olefins serve asco-monomers during polymerization of ethylene and/or propylene catalyzedby the second component. Of course, it is also expected thatoligomerization of these C₄–C₉ olefins with or without additionalethylene and/or propylene incorporated can also take place. Depending onthe catalyst system and reaction conditions selected, products ofvarious characteristics can be produced in accordance with thedisclosures of the present invention.

Examples of suitable ethylene and/or propylene dimerization and/ortrimerization catalyst include, but are not limited to, those comprisinga metal-tridentate ligand complex such as those represented by FORMULAB, wherein preferably the metal is selected from the group consisting ofCr, V, Mn, Ni, and/or mixtures thereof. It is more preferred that themetal M is or consists essentially of chromium (Cr), Q¹, Q², and Q³ areall nitrogen (N), both R² and R⁴ have the stricture of FORMULA C (i.e.phenyl groups), R¹¹ is preferably selected from H, methyl, ethyl,n-propyl, iso-propyl, and n-butyl groups, and R¹⁵ is H.

Examples of suitable Ziegler or Ziegler-Natta type catalysts for thesecond component include, but are not limited to those disclosed inGregory G. Hlatky, Chemical Reviews, 100, pp 1347–1376 (2000). Thecatalysts can be either “metallocene” or “non-metallocene” type. Someexamples can be found in Gibson et al, Angew. Chem. Int'l Ed., 38, 428(1999); and Pullkat et al, Catal. Rev.—Sci. Eng., 41(3 &4), 389–428(1999).

Examples of metallocenes or metallocene precursors suitable for use asthe second component of the multi-component catalyst system include, butare not limited to those based on cyclopentadienyl or modifiedcyclopentadienyl ligands. Non-liming examples can be found in manypublications such as Waymouth et al, Chemical Reviews, 98, 2587–2598(1998); Alt et al, J. Mol. Cat. A: Chemical 165, 23–32 (2001); Alt etal. Chem. Rev., 100, 1205–1222 (2000); and Ittel et al, Chem. Rev., 100,1169–1204 (2000).

The metal-ligand complex of the present invention as disclosed hereinwith or without a support can be used to effect polymerization ofolefins, particularly in the presence of a co-catalyst. It should berepeated again that, as already defined earlier, the term polymerizationis used herein broadly to include dimerization, trimerization, and/oroligomerization. Thus, the products could be dimers, trimers, oligomers(some of them are described herein as wax or waxes which contain abouttwenty to about sixty or more carbons), polymers and/or mixturesthereof. Under suitable conditions, the products obtained arecharacterized by having a Schulz-Flory constant (K) in the range of fromabout 0.4 to about 0.98, preferably from about 0.5 to about 0.9, morepreferably from about 0.55 to about 0.8.

The multi-component catalyst system is also useful in polymerizingolefins, particularly lower alpha-olefins in the presence of anorganometallic co-catalyst. While not bound by a particular theory, itis believed that the ethylene and or propylene dimers and or trimersproduced by the first component are incorporated as co-monomer(s) intothe polymer products produced by a co-polymerization catalyzed by thesecond component polymerization catalyst. The second component can bemixed with the first component followed by contacting with a suitableco-catalyst; or the second component can be added, with or withoutadditional co-catalyst, to the polymerization reactor after some initialreaction (such as ethylene or propylene dimerization reaction) hasalready taken place. When the multi-component catalyst is used and theolefin is selected from ethylene and propylene, the product is usuallycharacterized by being a polyethylene (PE), low-density polyethylene(LDPE), linear low density polyethylene (LLDPE), polypropylene (PP),waxes, and the like, and mixtures thereof. The products are particularlycharacterized by having branching along the polymer chain. Suchbranching may be identified or characterized by nuclear magneticresonance (NMR), gas chromatography (GC), thermal properties, or manyother methods known to one skilled in art, which are used tocharacterize co-polymers.

For most polymerization reactions, co-catalysts are used for supported,unsupported metal complexes or mixtures thereof. Many co-catalysts canbe used for the present invention to activate the catalyst or to providebetter polymerization activity/selectivity or other properties. Suitableco-catalysts include, but are not limited to organometallic compounds(monomeric or oligomeric metal alkyls, metal aryls, metal alkyl-aryls,with or without other moieties such as halide or alkoxide) comprising atleast one of the metals selected from the group consisting of B, Al, Ga,Be, Mg, Ca, Sr, Ba, Li, Na, K, Rb, Cs, Zn, Cd, and Sn. These arereferred to as organoboron, organoaluminum, organogallium,organoberyllium, organomagnesiu, organocalcium, organostrontium,organobarium, organolithium, organosodium, organopotassium,organoribidium, organocesium, organozinc, organocadmium and organotincompounds respectively. The only requirement in these compounds is thatthere is at least one carbon-metal bond like alkyl-M, aryl-M, anddelocalized carbon-containing moiety (for instance a cyclopentadienylgroup, C₅H₅ ⁻)-M bond. As it will become clear later, there may be othergroups such as halide, alkoxide and other similar groups. There also maybe more than one metal atom in these organometallic compounds. A generalcharacter is that they are active enough to reduce the oxidation statesof the metals in the metal-tridentate complex, or metallocene precursor,or Ziegler catalyst precursor, or Ziegler-Natta catalyst precursors.Preferred examples of suitable co-catalysts include, but are not limitedto organoaluminum compounds (such as aluminum alkyl compounds, with orwithout halides, alkoxides or other ligands or moieties), organoboroncompounds, organolithium compounds, organotin compounds, and mixtures orsolutions (many commercial materials are in solvents such as alkanes oralcohols) thereof. Organoaluminum compounds in all forms are morepreferred for their chemical properties, physical properties, commercialavailability, and costs.

More specific and preferred, but non-limiting, examples aretrimethylaluminum, triethylaluminum, diethylaluminum chloride,diethylaluminum ethoxide, diethylaluminum cyanide, diisobutylaluminumchloride, triisobutylaluminum, t-butyl alumoxanes, ethylaluminumsesquichloride, alumoxanes such as MAO (methylalumoxane), modifiedmethylalumoxane (MAO which contains other aluminum alkyl species ormoieties), dimethylboron bromide, methylboron dibromide, tributylboron,tributyltin chloride, tetra-n-propyltin, tetra-n-butyltin, and mixturesthereof. These materials can be purchased from commercial sources orprepared in accordance with published methods that are known to thoseskilled in the art. As already mentioned, these materials, particularlythose purchased from commercial sources, may further contain solventslike toluene, hexane, alcohols, etc. These solvents generally do notinterfere with the olefin polymerization reactions of this invention.

The relative amount of a co-catalyst to a catalyst is the range of fromabout 10,000:1 to about 1:10,000, preferably from about 5.000:1 to about1:5,000, more preferably from about 2,000:1 to about 1:2,000, all beingmolar ratios. In the case of the multi-component catalyst system, therelative amount of the first component to the second component is in therange of from about 0.001:1 to about 1:0.001; preferably 0.01:1 to1:0.01; more preferably from 0.1:1 to 1:0.1; all being molar basis. Therelative amount of a co-catalyst to the total amount catalyst in themulti-component catalyst system is the range of from about 10.000:1 toabout 1:10,000, preferably from about 5,000:1 to about 1:5.000, morepreferably from about 2,000:1 to about 1:2,000, all being molar ratios.

The co-catalyst(s) can be added to the metal-bidentate, -tridentate, ormulti-dentate complexes (catalyst) in any manner known in the art. Forinstance, the catalyst and the co-catalyst can be mixed first beforebringing in contact with a feed comprising an olefin or an olefinmixture. In the alternative, the co-catalyst can be mixed with theolefin-containinig feed first before this mixture is mixed with themetal-ligand complex catalyst. Many other modifications are possible. Asalready described above, in a multi-component catalyst system, thesecond component, with or without additional co-catalyst, may bepre-mixed with the first component, or it can be added to the reactorafter some or all of the initial dimerization and/or trimerizationreaction of ethylene and/or propylene is completed.

Many different olefins can be polymerized or co-polymerized (includingdimerization, co-dimerization, trimerization, co-trimerization, otheroligomerizations or co-oligomerizations) using the catalyst system ofthis invention and all these are within the scope of this invention.Examples include, but are not limited to ethylene, propylene, 1-butene,cis-2-butene, trans-2-butene, butadiene, isoprene, 1,3-pentadiene,1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene,4-vinylcyclohexene, norbornadiene, ethylidenenorbornene,vinylnorbornene, C₅ and higher olefins such as 1-petene,3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-octadecene, cyclopentene,methylcyclopentene (1-, or 2-, or 3- and mixtures), vinylcyclohexane,norbornene, vinyl aromatics such as styrene, o-methylstyrene,m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene,p-t-butylstyrene, divinylbenzene, 1-vinylnaphthalene,2-vinylnaphthalene, 2-vinylpyridiene, 3-vinylpyridine, 4-vinylpyridine,and the like, and mixtures thereof.

The product of the polymerization reaction most often comprises (co-)dimers to polymers, depending on the catalyst, the co-catalyst if any,the feed and other reaction conditions. In a preferred embodiment ofthis invention, the product comprises primarily terminal (i.e. α-)olefin products, linear or branched or mixtures thereof. Thedistribution of various compounds in the product depends on the reactionconditions, feed composition as well as the catalyst, includingco-catalyst. It is preferred to have narrow distribution of products,particularly for dimerization and trimerization reactions. Productseparation and purification will be easier if there are fewer compoundsin the product. For ethylene dimerization reactions, a typical productcontains primarily 1-butene. It is preferable to have 1-butene in excessof 98% among the butene isomers. It is more preferable to have 1-buteneof 99% or higher purity among the butene isomers.

The polymerization process or reaction, as previously defined to include(co-) dimerization, (co-)trimerization or other oligomerizations of oneor more olefins, may be carried out in any suitable mode or physicalform. For example, the reaction can be homogeneous, heterogeneous or acombination thereof. The polymerization process may be carried out in aslurry phase, gas phase, liquid phase, super-critical phase, or thelike, and combinations thereof. The polymerization can be carried out ina batch mode, continuous mode, semi-continuous mode or any other mannersknown to one skilled in the technology.

Because of the reactivity of metal-multidentate ligand complex and/orthe co-catalyst used for the polymerization reaction or for otherconsiderations, it is generally preferred to carry out in a non-reactiveor inert atmosphere the reactions—complex preparation andrecovery/purification (if any), activation, olefin polymerization, orpost polymerization treatments (such as to deactivate the entirecatalyst system or product recovery/purification). Sometimes it is alsopreferred to have some hydrogen in the system. Certainly, if theproducts or the reaction systems are not affected by oxygen and/or waterand there are no other safety concerns under the reaction conditions,then it is more convenient and cost effective to carry out certainindividual steps in air.

The polymerization reaction was carried out in a suitable reactor underconditions effective to produce the desired product. The importantreaction parameters include, but are not limited to, themetal-multidentate ligand complex, the metallocene and/or metalloceneprecursor if used, the co-catalyst, ratio of co-catalyst to thecatalyst, the feed, the medium (i.e. solvent) if one is used, reactiontemperature, reaction time, olefin partial pressure if it is a gas orhas a substantial vapor pressure under the reaction condition,replenishment of consumed olefin if desirable, amount of co-monomer ifpresent, other reactants such as hydrogen desired, reactive impurities(such as oxygen and water) in the reaction system, and the productwork-up procedure.

If the olefin monomer is a gas under the conditions, such as ethylene,then a suitable partial pressure is in the range of from about 0.1 psia(0.7 kPa) to about 2,500 psia (17,250 kPa), preferably 0.2 psia (1.4kPa) to 2,000 psia (13,800 kPa), more preferably from 0.5 psia (3.4 kPa)to 1,500 psia (10,300 kPa). Because the total system pressure willdecrease as the gaseous olefin(s) is(are) polymerized or consumed, onecan continue to add more monomer(s) to the reactor at a set rate (suchas a continuous flow of the monomer to the reactor), add differentmonomers, if more than one, at different rates, add more monomer(s) ondemand to maintain a certain system pressure, add a second differentmonomer or monomer mixtures to the reactor, let the system pressuredecrease, any other choices known to those skilled in the art, or acombination thereof. If no additional monomer is needed or desired,gases inert to the reaction mixture may be used to make the necessarypressure.

The polymerization temperature is in the range of from about 0° C. toabout 150° C., preferably from about 10° C. to about 120° C., morepreferably from 20° C. to 75° C. A suitable temperature is determined bya number of factors, such as catalyst stability, catalyst activity, themonomer or monomers to be polymerized or co-polymerized, the propertiesof the co-catalyst, and others.

The olefin monomer(s) may be pre-mixed or added simultaneously to thepolymerization reactor, or added sequentially to the reactor or meteredinto the reactor in some other manner. The olefin monomer(s) can also beadded as needed (on demand) to maintain a certain system pressure. Theolefin monomer(s) can also be added continuously at certain rate. Or,the olefin monomers can also be added at the beginning and then let thembe consumed without any additions. All these may be done at fixedreaction parameters or variable parameters such as pressure ramp ortemperature ramp. Combinations of some of these may also be used.

The olefin monomer(s), the metal-ligand complex or the multi-componentcatalyst system, the co-catalyst (if used), and any other materials,such as a medium, may be mixed or contacted with one another accordingto the sequences or orders known to those skilled in the art. Certainly,the first component, the second component, and other components (if any)and the co-catalyst may be brought into contact with one another in anyorder or sequence or simultaneously.

The following examples illustrate preparations of exemplary ligands,preparations of certain metal-multidentate ligand complexes, andpolymerization of olefins by using catalysts comprising the complexesand co-catalyst, and analyses used to characterize different productsfrom these reactions.

EXAMPLE 1

This example shows a typical preparation method of a tridentate ligandlike 6-[1-{(2,6-dimethylphenyl)imino}ethyl]-2-acetylpyridine. 3.0 g(18.4 mmol) of 2,6-diacetylpyridine and 2.3 ml (18.7 mmol) of2,6-dimethyl aniline were added to a flask with a stirbar and 20 ml ofanhydrous methanol. Several drops of glacial acetic acid were added, andthe reaction was heated with stirring for 3 days at 55° C. The reactionflask was then placed in a freezer at −20° C., resulting in theformation of yellow, needlelike crystals. These crystals were removed byfiltration and washed with cold methanol (yield=1.15 g, 23.5%).

EXAMPLE 2

The following is one example of demonstrating how a chromium basedcomplex—chromium(II)6-[1-{(2,6-diisopropylphenyl)imino}ethyl]-2-acetylpyridine chloride(with THF) was prepared:

A sample of 1.0 gram of6-[1-{(2,6-diisopropylphenyl)imino}ethyl]-2-acetylpyridine and 382 mg ofchromium chloride (CrCl₂, obtained from Aldrich Chemical Company) weretransferred into a flask in a drybox under argon. Anhydrous tetrahyfuran(THF), about 50 ml, was added to this mixture. The mixture was stirredovernight under argon. The mixture was then allowed to stand for threedays, followed by addition of about 100 ml of n-pentane. A grayishpurple solid was isolated by filtration in air. The filtrate was green.The recovered solid was further washed with n-pentane and dried. Totalyield was 1.237 grams (90% of theoretical yield).

This metal complex was used for the polymerization reaction Entry 9 andEntry 13 in TABLE I.

EXAMPLE 3

A similar method was used successfully to prepare a chromium(II)chloride complex containing6-[1-{(2,6-dimethylphenyl)imino}ethyl]-2-acetylpyridine. The complex hada light purple color. The amount of tridentate ligand used was 267 mgand CrCl₂, 120 mg was obtained from Strem Chemical Company.

This metal complex was used for the polymerization reaction Entry 8 inTABLE 1.

EXAMPLE 4

The polymerization reactions were carried out in the following manner.All of the solvents such as anhydrous THF, heptane and cyclohexane werepurchased from Aldrich Chemical Company and stored over molecular sievesbefore use. 1-hexene was obtained as a commercial grade of ChevronPhillips' NAO's and dried over molecular sieves. MMAO-3A was purchasedfrom Akzo Nobel.

For small, low-pressure ethylene polymerization reactions, in an inert,oxygen and moisture free, atmosphere (such as a dry box filled withnitrogen or argon) the metal-ligand complex, such as achromium-tridentate ligand complex, a medium (polymerization solvent) ifone was used, and a stir-bar were placed in a flask. For amulti-component catalyst system, the second component was also added tothe flask at the same time in the experiments. As already pointed outearlier, the second component also may be added later to a reactor withor without using additional co-catalyst such as aluminum alkyls. Theflask was transferred to a Schlenk manifold and placed under acontinuous ethylene purge. The flask contents were stirred rapidly forseveral minutes to saturate the solvent (such as heptane) with ethyleneand to break apart any small chunks of the complex. A co-catalyst suchas MMAO-3A from Akzo Nobel was added via a syringe while the stirringcontinued. Optionally, a cooling bath could be used to control and/ormaintain the desired reaction temperature. For reactions in which lightolefins (such as butenes) were the primary products, ethylene wascontinuously purged through and out of the reaction flask. For thereactions waxes and/or higher molecular weight polyethylenes (PE) wereproduced, ethylene was added “on demand.”

For reactions carried out at a pressure higher than about ambientpressure, a one-liter Zipperclave™ reactor fro Autoclave Engineers wasused. The reactor should be clean and dried appropriately. Themetal-ligand complex was dissolved in a small amount of solvent such asmethylene chloride in a breakable thin-glass tube, which was then boundto the stirrer shaft of the reactor. The reactor was then evacuated,charged with a medium if one used and a co-monomer if one is used, and aco-catalyst. If the co-monomer is a gas under ambient conditions, itwould be added via a gas inlet. The olefin (such as ethylene) was thenadded and the stirred shaft was started, thus breaking the breakablethin-glass tube, thus contacting the metal-ligand complex with theco-catalyst and the olefin. For olefins such as ethylene, propylene orbutene which are gases under ambient conditions, they were added throughan inlet tube. It was preferred, particularly for ethylene, that theolefin was added “on demand,” i.e. added enough to maintain a certainpre-determined pressure or pressure profile. The reactor temperature wasmaintained by passing a coolant through and cooling coil inside thereactor. After the desired reaction period was reached, it was moreconvenient to add a deactivating agent to “kill” the catalyst system forproduct work-up. For most reactions, and particularly whenorganoaluminum such as MAO or MMAO co-catalysts were used, an acidifiedmethanol solution was used for this purpose. The product mixtures werethen removed from the reactor, followed by filtration, washing or othercommon product purification techniques. The products were analyzed bygas chromatography (GC) and other analytic techniques or methods knownto those skilled in the art.

Results from such polymerization reactions are shown in TABLE I. All ofthe catalysts contained chromium, and MMAO was used as the co-catalyst.Q¹ is nitrogen. Q² and Q³ were both nitrogen for Type 1; Q² was nitrogenand Q³ was oxygen for Type 2. R¹ and R³ (when present in Type 1) wererepresented by FORMULA C with R¹¹ and R¹⁵ shown in the Table. Thereactions were carried out at temperatures between 25° C. (ambienttemperature) and 100° C. Ethylene pressure was in the range of from 15psia (100 kPa) to 415 psia (2,860 kPa).

Results from polymerizations using a multi-component catalyst system areshown in TABLE II. Unless otherwise specified, the designations andabbreviations are used to indicate the same. See more detaileddescriptions of the two entries below. The metallocene precursorC₅(CH₃)₄Si(CH₃)₂N(t-Bu)TiCl₂ was prepared according to the method inliterature.

TABLE* I

TABLE I Polymerization of Ethylene and α-Olefins UsingChromium-Tridentate Ligand Complexes Complex P_(ethylene)(psi), SolventRxn Prod.^(f) amount comonomer (medium) length Yield (g/g Cr EntryType^(a) R¹¹ R¹⁵ (mg) Al:Cr^(c) (amount)^(d) (ml)^(e) (min) T (° C.) (g)complex) Notes 1 1 H H 5.7 500 15 CyH(40) 30 35 n.d. n.d. rapidexotherm; mostly butene, heavily isomerized to c- and t-2-butene 2 1 MeH 6.1 400 15 CyH(40) 60 35 n.d. n.d. rapid exotherm, required cooling;mostly 1-butene, 99% purity 3 1 Et H 5.4 500 15 CyH(40) 80 35 n.d. n.d.rapid exotherm, 99% pure 1-butene 4 1 iPr H 4.6 500 15 CyH(40) 30 35n.d. n.d. rapid exotherm, 99% pure 1-butene, small amts. of higherolefins 5 1 t-Bu H 5.2 500 15 CyH(40) 180 25 1.9 370 major product is PE6 1 Me Me 6.7 500 15 CyH(40) 120 35 10.4 1550 C_(max)(GC)~C₄₈; SchulzFlory constant ~0.96 7 1 Me H 5.1 1100 400 CyH(200) 30 85 n.d. n.d. veryrapid exotherm, 99.6% 1-butene purity, small amt of hexenes, octenes, PE8 2 Me Me 18.0 160 15 heptane(50) 180 25 6.0 330 waxes 9 2 iPr iPr 21.0120 15 heptane(50) 180 25 1.2 60 heavy waxes 10 2 t-Bu H 6.3 500 15heptane(40) 60 25 1.1 180 heavy waxes/PE 11 2 Me Me 5.0 1150 400heptane(200) 60 80 101 20,200 α-olefin waxes, Schulz-Flory K~0.87 12 2Me Me 4.0 1150 400 heptane(200) 60 100 95 23,800 α-olefin waxes, K~0.8713 2 iPr iPr 15.0 225 400 heptane(200) 120 60 25.0 1670 heavy waxes, Mn= 750 14 2 Me Me 14.6 160 15, n.a. 360 25 1.8 100 gummy solid; 1-hexenesignificant C₆ (50 ml) incorp. by GC 15 2 Me Me 13.6 260 15, heptane(45)180 25 22.2 1520 waxes; 1-hexene significant C₆ (9 ml) incorp. by GC 162 Me M 13.6 260 15, Heptane (50) 1200 25 35.5 2610 Waxes 1-octadeceneSignificant C₁₈ (15 ml) incorporated Notes: ^(a)Type 1: Q¹, Q², and Q³are all nitrogen; Type 2, Q¹and Q² are nitrogen, and Q³ is oxygen; R¹and R³ (if present) are represented by FORMULA C. b) For example, 2-Hrepresents unsubstituted aryl rings for a Type I complex. ^(c)Molarratio of Al to Cr in the reaction. ^(d)Ethylene pressure, and amount ofcomonomer present (if applicable). ^(e)CyH is cyclohexane. ^(f)Prod. =productivity, which was not determined for reactions in which the majorproduct was butene.

TABLE II Entry 17 18 Type (First Component) 1 1 R¹¹ Me IPr R¹⁵ H HAmount (mg) 2.5 2.0 Al:Cr 2000 3000 Second Component g 2 R¹¹ — Me R¹⁵ —Me Amount (mg) 4.0 7.5 Al:Metal 1000 600 P_(ethylene) (psia) 15 15Solvent, or medium (ml) Heptane (40) Heptane (50) Reaction time (min) 60240 T(° C.) 30–35 25 Yield (g) 3.61 1.62 Productivity 900 170 (g/g Crcomplex) Notes PE PE Branching observed^(h) Branching observed^(h) g)C₅(CH₃)₄Si(CH₃)₂N(t-Bu)TiCl₂ ^(h)The branching, observed from gaschromatographic analyses is similar to Entry 15, where 1-hexene was usedas a co-monomer.

For Entry 1, where both R¹¹ and R¹⁵ are hydrogen (H), the butene productcontains substantial amount of cis- and trans-2-butenes. For Entry 14,there was substantial incorporation of 1-hexene in the products byanalyses. For Entry 15, there was substantial incorporation of 1-hexenein the products by analyses. For Entry 11, K was about 0.87. For Entry12, K was also about 0.87. For Entry 2, in the C₄ olefins, 1-butene wasin excess of 99% purity among the butene isomers; some low purity of C₆products. For Entry 7, in the C₄ olefins, 1-butene was about 99.6% pure;in the C₆ olefins, 1-hexene was about 93% pure. Entry 3 and Entry 4 alsogave 1-butene at 99% purity. Entry 16 showed the incorporation of 1-C₁₈olefin.

It can be seen from these results that a catalyst comprising thechromium metal complexes and an aluminum alkyl co-catalyst, MMAO, wereeffective in both polymerization and co-polymerization. Productscomprising high α-olefin concentrations (such as 1-butene and 1-hexene)were produced when all three coordinating sites are nitrogen and therewas a single ortho-substitution of on the phenyl ring as represented byFORMULA C. When the ortho-substitution was a large t-butyl group,polyethylene was produced.

Results in TABLE I also showed that catalysts comprising the chromiummetal complexes and a suitable aluminum alkyl, MMAO, were very active,having good productivity per gram of chromium.

Entry 17 in TABLE II shows that when a chromium tridentate ligand (type1, all three coordinating sites were nitrogen) complex was used incombination with a metallocene precursor, polyethylene (wax type) wasobtained with ethylene as the feed. The product was very similar to thatobtained in Entry 15, where 1-hexene was used as a co-monomer. GCanalysis showed branching on the polymer chains.

Entry 18 in TABLE II shows that when a chromium tridentate ligand (allthree coordinating sites were nitrogen) complex was used in combinationwith a different chromium tridentate ligand (type 2, Q¹ and Q² werenitrogen, Q³, oxygen) complex, polyethylene (wax type) was obtained withethylene alone. The product was very similar to that obtained in Entry15, where 1-hexene was used as a co-monomer. GC analysis showedbranching on the polymer chains.

The examples herein are provided only for the purpose of illustratingthe embodied invention. They are not intended and should not be treatedas to limit the spirit and scope of the instant invention, which isdefined solely by the specification and claims.

1. A process for making a product, comprising contacting at least oneolefin in a feed with a catalyst under reaction conditions followed byrecovering the product, wherein the catalyst comprises ametal-tridentate ligand complex having a FORMULA B:

wherein Q¹, Q², and Q³: independently selected from O, S, N, and P; R¹and R³: independently selected from H, C₁ to C₂₀ alkyl groups, 1-, 2- or3-ring aryl groups and substituted aryl groups; R² and R⁴: if Q² or Q³is O or S, none, if Q² or Q³ is either N or P, independently selectedfrom H, C₁ to C₂₀ alkyl groups, 1-, 2- or 3-ring aryl groups andsubstituted aryl groups; R⁵, R⁶, and R⁷: independently selected from H,C₁ to C₂₀ alkyl groups; M: a first transition metal selected from thegroup consisting of Cr, Mn, V, Ti, Zr, Hf, Ta, and mixtures thereof; L:each L independently selected from the group consisting of F, Cl, Br, I,C₁ to C₂₀ alkyl, C₅ to C₁₄ aryl, nitrate, OR²¹, OC(═O)R²²; R²³; CN; SCN,CO, H, wherein R²¹, R²², and R²³ are independently selected from thegroup consisting of H, C₁ to C₂₀ alkyl groups, substituted alkyl groups,1-, 2- or 3-ring aryl groups, substituted aryl groups, and silyl groups;solvent: selected from the group consisting of ethers, polyethers,esters, alcohols, halogenated hydrocarbons, and mixtures thereof; q: 0–5(integer) to balance overall electrical charge; and m: 0–10 (integer orfractional).
 2. The process of claim 1, wherein the olefin in the feedcomprises at least one α-olefin and Q¹, Q², and Q³ comprise at least twodifferent elements.
 3. The process of claim 2, wherein the transitionmetal (M) consists essentially of an element selected from the groupconsisting of manganese, chromium, vanadium, and mixtures thereof. 4.The process of claim 3, further comprising a co-catalyst comprising oneor more organometallic compounds selected from organoaluminum compound,organoboron compound, organogallium compound, organozinc compound,organocadmium compound, organotin compound, organolithium compound,organosodium compound, organopotassium compound, organorubidiumcompound, organomagnesium compound, organocalcium compound, and mixturesthereof; and wherein the α-olefin in the feed is selected from the groupconsisting of ethylene, propylene, 1-butene, cis-2-butene,trans-2-butene, 1,3-butadiene, 1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-octene, 1-octadecene, 1,5-hexadiene, 1,4-hexadiene, styrene,o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene,p-t-butylstyrene, and mixtures thereof; and the product comprisesprimarily terminal olefins, which are linear, branched or mixturesthereof.
 5. The process of claim 3, wherein Q¹ and Q² are nitrogen, Q³is oxygen, and R⁴ does not exist; R¹ and R³ are independently selectedfrom C₁ to C₅ alkyl groups; R² is selected from 1-ring aryl groups; R⁵R⁶, and R⁷ are independently selected from H and C₁ to C₅ alkyl groups;and each L is independently selected from F, Cl, Br, I, alkyl, aryl andmixtures thereof.
 6. The process of claim 5, wherein R² has a structureof FORMULA C:

R¹², R¹³, and R¹⁴ are H; and R¹¹ and R¹⁵ are selected independently fromthe group consisting of H, methyl, ethyl, n-propyl, and iso-propylgroups.
 7. The process of claim 1, wherein M consists essentially of anelement selected from the group consisting of chromium, vanadium,manganese, and mixtures thereof; Q¹ and Q² are nitrogen, Q³ is oxygen,and R⁴ does not exist; R¹ and R³ are independently selected from C₁ toC₅ alkyl groups; R² is selected from 1-ring aryl groups; R⁵ R⁶, and R⁷are independently selected from H and C₁ to C₅ alkyl groups; each L isindependently selected from F, Cl, Br, I, alkyl, aryl, and mixturesthereof.
 8. The process of claim 7, wherein R² has a structure ofFORMULA C:

R¹², R¹³, and R¹⁴ are H; and R¹¹ and R¹⁵ are independently selected fromthe group consisting of H, methyl, ethyl, n-propyl, and iso-propylgroups.
 9. The process of claim 1, further comprising a co-catalystselected from at least one aluminum alkyl compound; and wherein theolefin is selected from ethylene, propylene, 1-butene, 1-pentene,1-hexene, 1-heptene, 1-octene, 1-octadecene, and mixtures thereof; thetransition metal consists essentially of chromium; q is 2; thetridentate ligand is selected from the group consisting of6-[1-{(2,6-dimethylphenyl)imino}ethyl]-2-acetylpyridine,6-[1-{(2,6-dimethylphenyl)imino}ethyl]-2-acetylpyridine, and mixturesthereof; and the product comprises terminal olefins, which are linear,or branched, or mixtures thereof.
 10. The process of claim 1 wherein theat least one olefin is ethylene; the product is butene; and Q¹, Q², andQ³ are nitrogen.
 11. The process of claim 10, wherein the ethylene has apartial pressure in the range of from about 0.1 psia (0.7 kPa) to about2500 psia (17,250 kPa) and the reaction conditions comprise atemperature in the range of from about 0° C. to about 150° C.
 12. Theprocess of claim 11, wherein the transition metal consists essentiallyof an element selected from the group consisting of chromium, vanadium,manganese, and mixtures thereof; and further comprising a co-catalystcomprising at least one organometallic compound selected from the groupconsisting of organoaluminum compound, organoboron compound, organotincompound, and mixtures thereof.
 13. The process of claim 12, wherein thetransition metal consists essentially of chromium; q is 2; R¹¹ isselected from the group consisting of methyl, ethyl, n-propyl, andiso-propyl groups; R¹⁵ is H; and the product comprises 1-butene of 99%or higher purity among butene isomers.
 14. The process of claim 12,wherein the transition metal consists essentially of chromium; q is 2;R¹¹ and R¹⁵ are both H; and the product comprises butene isomermixtures.
 15. The process of claim 2, wherein the product ischaracterized by having a Schulz-Flory constant (K) in the range of fromabout 0.5 to about 0.9; and further comprising a co-catalyst comprisingone or more organometallic compounds selected from organoaluminumcompound, organoboron compound, organogallium compound, organozinccompound, organocadmium compound, organotin compound, organolithiumcompound, organosodium compound, organopotassium compound,organorubidium compound, organomagnesium compound, organocalciumcompound, and mixtures thereof.
 16. The process of claim 15 wherein thetransition metal (M) consists essentially of an element selected fromthe group consisting of manganese, chromium, vanadium, and mixturesthereof; and Q¹ and Q² are nitrogen, Q³ is oxygen, and R⁴ does notexist; R¹ and R³ are independently selected from C₁ to C₅ alkyl groups;R² is selected from 1-ring aryl groups; R⁵ R⁶, and R⁷ are independentlyselected from H and C₁ to C₅ alkyl groups; and each L is independentlyselected from F, Cl, Br, I, alkyl, aryl and mixtures thereof.
 17. Theprocess of claim 16 wherein the α-olefin in the feed is selected fromthe group consisting of ethylene, propylene, 1-butene, cis-2-butene,trans-2-butene, 1,3-butadiene, 1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-octene, 1-octadecene, 1,5-hexadiene, 1,4-hexadiene, styrene,o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene,p-t-butylstyrene, and mixtures thereof; and the product comprisesprimarily terminal olefins, which are linear, branched or mixturesthereof.
 18. The process of claim 1, wherein the at least one olefincomprises ethylene, propylene, and mixtures thereof; themetal-tridentate ligand complex having the FORMULA B wherein Q¹, Q², andQ³ are nitrogen is a first catalyst component; and further comprising atleast one second catalyst component having a second transition metalselected from the group consisting of a Ziegler-Natta catalyst, aprecursor of the Ziegler-Natta catalyst, a metallocene, a precursor ofthe metallocene, a second metal-tridentate ligand complex having theFormula B wherein Q¹, Q², and Q³ are independently selected from O, S,N, and P and are not all the same, and mixtures thereof.
 19. The processof claim 18, wherein the first transition metal is selected from thegroup consisting of manganese, chromium, vanadium, nickel, and mixturesthereof; and the second transition metal is selected from the groupconsisting of titanium, zirconium, hafnium, vanadium, and mixturesthereof.
 20. The process of claim 19, further comprising a co-catalystcomprising at least one organometallic compound selected from the groupconsisting of organoaluminum compound, organoboron compound,organogallium compound, organozinc compound, organocadmium compound,organotin compound, organolithium compound, organosodium compound,organopotassium compound, organorubidium compound, organocesiumcompound, organomagnesium compound, organocalcium compound,organostrontium compound, organobarium compound, and mixtures thereof.21. The process of claim 20, wherein the product is characterized byhaving branching along main polymer chains and is selected from thegroup consisting of polyethylene (PE), low density polyethylene (LDPE),linear low density polyethylene (LLDPE), polypropylene (PP), wax, andmixtures thereof.